Anthraquinone vat dyestuffs



Patented Apr. 13, 1948 ais'sgszc I 'ANTHRAQUINONE var DEESTUF-FS Walter Kern, Sissach,

Switzerland, assignor to Society. of '(lhemical Industry in Basie, Basel, Switzerland, a Swiss firm 7 No Drawing. Application October 2, 1944, Serial No. 556,908. In Switzerland November 1, 1943 According to this invention valuable vat dyestuffs are prepared by introducing an acylamino group into each of the 1- and 4-positions of an anthraquinone, at least oneof the said acylamino groups cont'ainingthe radical of an arylsulfone-aryl carb'oxylic acidtas acyl radical.

Anthraquinones serving as starting materials for the present process may contain, for example, also such substituents as are usual in vat dyestuffs of this kind, e. g. halogens.

The arylsulfone-aroylamino groups which are to be introduced into such compounds may contain as aryl radicals for example radicals of the benzene series. In the arylsulione-arylcarboxylic acids from which they are derived the caroxyl group may occupy various positions with respect to the arylsulfone group, for example, the meta-position and preferably the para-position. Examples of such carboxylic acids are 3-phenylsulfone-benzene-l-carboxylic acid and 4-phenylsulfone-benzene-l-carboxylic acid.

The arylsulfone-aroylamino groups can be introduced into the above mentioned v'attable compounds in several stages, for example by intro-i ducin'g at first amino groups into the positions many cases it is also possible to introduce arylsulione-aroylamino groups in one stage, by exchanging for example a substituent capable of being exchanged, such as halogen or nitro groups, for arylsulfone-aroylamino groups by treating with arylsulfone-aryl-carboxylic acid amides.

According to the present process preferably only one arylsulfone-aroylamino group is introduced into an anthraquinone nucleus, whereas the para-position to this group is occupied, for example previously or subsequently, by an acylamino group the acyl radical of which corresponds to a carboxylic acid free from sulfone groups, e. g, to an aromatic carboxylic acid, such as benzoic acid. For example l-aminoi-benzoylaminoanthraquinone can be caused to react with 1 mol. of 4-phenylsulfone-benzene-l-carboxylic acid chloride or e. g. 1-halogen-4-benzoylaminoanthraquinones can be reacted with 1 mol. of the corresponding acid amide.

The products thus obtained can be used in known manner for dyeing and printing a great variety of animal and, especially, vegetable fibers,

4 Claims. (Cl. 260-372) For example, 1 z l-di-aminoanthra such as cotton, linen, artificial silk, and staple fiber from regenerated cellulose (and .superpolyamides. Furthermore, in the form of their leucoester salts of sulfuric acid obtainable in the usual f5: manner they can be used for dyeing and printing by the usual methods employed or this class of dyestufis.

The following examples illustrate the invention, but are not to be regarded as limiting it .in anyway, the parts being "bywei ght:

I Example 1 13 parts of l-phenyls'ulf'one-benzene-l-carboxylic acid are suspended in 320' parts of anhydrous ortho-dichlorobenzene and after adding 49 parts of thionyl chloride and a small quanti ygof pyridine, the mixture is maintained first for 1 .hour at 80-90 C. and then for a further hour'at 100-110 C'., while stirring. The thionylchloride in excess and some ortho-dichlorobenzene are distilled off and the temperature is reduced to 100 0., 17.25 parts of l-amino-4-benzoy'laminoanthraquinone are added and stirring is continued for 2 hours at 170-175" C., finally for hour at the boil. When cold the precipitated 1-(4- phenylsulfone benzoylamino) -4-benzoylaminoanthraquinone is filtered off, washed with alcohol and dried. The dyestufl obtained in very good yield iorm's red crystals melting at 363-365 3'0 (3.:which dissolve in concentrated sulfuric acid to a red solution and dye cotton very fast, bril liant red tints from a black-violet vat.

A similar dyestufl is obtained by using 3-phenylsulfone-benzene-l-carboxylic acid, instead of 4-phenylsulfone-benzene-1-carboxylic a c i d Bluer shades are obtained by reacting l-amlno- 4-benzoylamin oanthraquinone with 4-(4'-chlorophenylsulfone)-benzene-1-carboxylic acid or 4-(4-methoxy phenylsulfone) -benzene-1-carboxylic acid.

In all the dyestuffs of this example the benzoylamino group in 4-position of the anthraquinone nucleus may be replaced by substituted benzoylamino groups, such as groups containing the radical of 3- or 4-chlorobenzoic acid, anisic acid or para-toluic acid. Very similar results are also obtained with dyestuffs containing halogen in the anthraquinone nucleus, for example chlorine in 6-position.

Ewample 2 2.6 parts of 4-phenylsulfone-benzene-l-carboxylic acid are suspended in parts of anhydrous ortho-dichlorobenzene and after adding 8 parts of thionylchloride the mixture is maintained 55 first for 1 hour at -90 C. and then for a fur- PATENT OFFlCE 3 4 ther hour at 100-110 0., while stirring, where- 2. A vat dyestufi which is the anthraquinone by solution occurs. The thionylchloride in excess substitution product of the formula and some parts of ortho-dichlorobenzene are distilled off, the temperature is reduced to 100 C. NIH-C OC s:-C

and 1.2 parts of 1:4-diaminoanthraquinone are introduced. In order to complete the reaction,

stirring is continued for 2 hoursat 170-1'75 C.

and for 4 hour at the boil, whereupon the dyestufi, after cooling, is precipitated as red needles. I

These are filtered, washed with alcohol and dried. joy; 0 NH The 1:4-di-(4'- henylsulfone-benzoylamino) -an s I 0 thraquinone which is obtained in very good yield is dissolved in concentrated sulfuric acidto a 3, A v t. dyestufi hi h is th anthraquinone red-orange solution and dyes cotton fast red tints-- substitution product of the formula fromagreenvat. t

A similar dyestufi? is obtained if 1:4-diaminoo NH-O o gsor-ool anthraquinone is condensed with. 4-(4'-chloro-" V. phenylsulfone)-benzene-1-carboxylic acid.

Example 3 2 parts of the dyestuif obtained according to m the first paragraph of Example 1. are thoroughly 0 NH 7 stirred with 300parts of water and 8 parts by O volume of caustic soda solution of 36 B. and

the solution is vatted by addition of 4 parts of sodiumhydrosulfite at'about 0. This stock ggggfifgfjfii f gfig figaf vat is added to a dye-bath containing in 2700 parts of water '7 parts by volume of caustic soda I 0 AC O solution of 36 B. and 4 parts of sodium hydro- II sulflte. 100 parts of cotton are introduced into 30 the dye-bath at 25C., 75 parts of common salt are added after /4 hour and dyeing is continued for 1 hour at 25-30 C. The cotton is squeezed,

oxidized in the air, rinsed, acidified, rinsed again 0 7 NH soaped at the boil. The goods are dyed very I 0 fast red tints. i

What I claim is: 1..A vat dyestuff which is an anthraquinone WALTER KERN. substitution product of the formula 0 REFERENCES CITED The following references are of record in the NH-CO@SOa-@X file of this patent:

UNITED STATES PATENTS Number Name Date 2,190,751 Zerweck et a1 Feb. 20, 1940 I p 2,356,061 Irving et a1. Aug. 15, 1944 0 N FOREIGN PATENTS wherein X stands fora memberselected from the group consisting of hydrogen, chlorine and methoxy.

Number Country Date 656,488 Germany Feb. 11, 1938 

